Two 3D metal–organic frameworks with different topologies, thermal stabilities and magnetic properties

Gao, Ting; Wang, Xiaozhu; Gu, Hao-Xue; Xu, Yan; Shen, Xuan; Zhu, Dunru

doi:10.1039/c2ce25442e

Cited by 34 publications

(9 citation statements)

References 68 publications

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“…The magnetic properties of MOFs and coordination polymers are of continuous interest. 2,[42][43][44] The ground state of Co(II) ions (d 7 ) in a tetrahedral environment is 4 A 2 , for which the orbital angular momentum contribution is a second-order effect, and so, the spin-only model can be used to describe the magnetic behaviour of compound 1. 45 Fig.…”

Section: Magnetic Properties Ofmentioning

confidence: 99%

Bifunctional pyrazolate–carboxylate ligands for isoreticular cobalt and zinc MOF-5 analogs with magnetic analysis of the {Co4(μ4-O)} node

et al. 2013

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The ditopic ligands 3,5-dimethyl-pyrazolate-4-carboxylate,-Me 2 pzCO 2 -, and 4-(3,5-dimethyl-1H-pyrazol-4yl)benzoate, -Me 2 pzC 6 H 4 CO 2 -, combine a pyrazolate and carboxylate functionality in axial orientation and lead to porous cobalt or zinc azolate-carboxylate frameworks that have the same cubic pcu-a topology and {M 4 (μ 4 -O)} nodes (M = Co, Zn) as MOF-5 and other IRMOFs. The microporous networks [M 4 (μ 4 -O)(Me 2 pzCO 2 ) 3 ] (M = Co, Zn) with the short linker exhibit a solvent-induced gate effect, evidenced by gas desorption hysteresis due to small pore apertures of 2.8 Å diameter together with small amounts of high-boiling solvent remaining in the activated samples. For [Co 4 (μ 4 -O)(Me 2 pzCO 2 ) 3 ], the low-pressure H 2 storage capacity (1.7 wt%, 1 bar , 77 K) is higher than for MOF-5, and the CO 2 uptake of 20.8 wt% puts it among the top MOFs for low-pressure CO 2 sorption even though the BET surface is less than 1000 m 2 g −1 . The analysis of the magnetic properties of [Co 4 (μ 4 -O)(Me 2 pzCO 2 ) 3 ] takes into account the distribution of tetrahedra resulting from the disorder of the pyrazolate-carboxylate linker. An antiferromagnetic coupling observed for [Co 4 (μ 4 -O)(Me 2 pzCO 2 ) 3 ] arises from the interactions of the cobalt(II) ions through the combined μ 4 -O + syn-syn carboxylate and μ 4 -O + pyrazolate bridges.

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Section: Magnetic Properties Ofmentioning

confidence: 99%

Bifunctional pyrazolate–carboxylate ligands for isoreticular cobalt and zinc MOF-5 analogs with magnetic analysis of the {Co4(μ4-O)} node

et al. 2013

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“…Second, MOFs possess a high degree of synthetic flexibility that allows their intrinsic electrical, optical, and mechanical properties to be tuned. 10 This has lead to a remarkable range of electronic, photonic, and magnetic behaviors: ferroelectric, 14,15 ferromagnetic, 16,17 antiferromagnetic, 18,19 low-k dielectrics, [20][21][22] proton- 23,24 and ion-conducting, 25,26 luminescent, [27][28][29] and non-linear optical properties 30,31 have been described. Although the vast majority MOFs are insulators, 32 a few semiconducting frameworks are known and theoretical predictions suggest many more are possible.…”

Section: Introductionmentioning

confidence: 99%

MOF-based electronic and opto-electronic devices

2014

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Metal-organic frameworks (MOFs) are a class of hybrid materials with unique optical and electronic properties arising from rational self-assembly of the organic linkers and metal ions/clusters, yielding myriads of possible structural motifs. The combination of order and chemical tunability, coupled with good environmental stability of MOFs, are prompting many research groups to explore the possibility of incorporating these materials as active components in devices such as solar cells, photodetectors, radiation detectors, and chemical sensors. Although this field is only in its incipiency, many new fundamental insights relevant to integrating MOFs with such devices have already been gained. In this review, we focus our attention on the basic requirements and structural elements needed to fabricate MOF-based devices and summarize the current state of MOF research in the area of electronic, opto-electronic and sensor devices. We summarize various approaches to designing active MOFs, creation of hybrid material systems combining MOFs with other materials, and assembly and integration of MOFs with device hardware. Critical directions of future research are identified, with emphasis on achieving the desired MOF functionality in a device and establishing the structure-property relationships to identify and rationalize the factors that impact device performance.

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“…The emphasis on technologies that harness the adsorptive properties of MOFs is no coincidence from the perspective of optoelectronic applications, because many of the typical organic linkers possess large HOMO–LUMO gaps that limit visible light absorption and charge transport. However, in addition to these “traditional” uses of porous materials, , MOFs hold potential for use as optoelectronic materials, with structures exhibiting a host of intriguing properties, including ferroelectric, , ferromagnetic, , antiferromagnetic, , proton- , and ion-conducting, , luminescent, , or nonlinear optical behaviors. , The challenge is to harness these properties in order to create emergent behavior at the device level.…”

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confidence: 99%

Guest-Induced Emergent Properties in Metal–Organic Frameworks

Allendorf

Foster

Léonard

et al. 2015

J. Phys. Chem. Lett.

163

180

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Metal-organic frameworks (MOFs) are crystalline nanoporous materials comprised of organic electron donors linked to metal ions by strong coordination bonds. Applications such as gas storage and separations are currently receiving considerable attention, but if the unique properties of MOFs could be extended to electronics, magnetics, and photonics, the impact on material science would greatly increase. Recently, we obtained "emergent properties," such as electronic conductivity and energy transfer, by infiltrating MOF pores with "guest" molecules that interact with the framework electronic structure. In this Perspective, we define a path to emergent properties based on the Guest@MOF concept, using zinc-carboxylate and copper-paddlewheel MOFs for illustration. Energy transfer and light harvesting are discussed for zinc carboxylate frameworks infiltrated with triplet-scavenging organometallic compounds and thiophene- and fullerene-infiltrated MOF-177. In addition, we discuss the mechanism of charge transport in TCNQ-infiltrated HKUST-1, the first MOF with electrical conductivity approaching conducting organic polymers. These examples show that guest molecules in MOF pores should be considered not merely as impurities or analytes to be sensed but also as an important aspect of rational design.

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Two 3D metal–organic frameworks with different topologies, thermal stabilities and magnetic properties

Cited by 34 publications

References 68 publications

Bifunctional pyrazolate–carboxylate ligands for isoreticular cobalt and zinc MOF-5 analogs with magnetic analysis of the {Co4(μ4-O)} node

Bifunctional pyrazolate–carboxylate ligands for isoreticular cobalt and zinc MOF-5 analogs with magnetic analysis of the {Co4(μ4-O)} node

MOF-based electronic and opto-electronic devices

Guest-Induced Emergent Properties in Metal–Organic Frameworks

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